Modified sulfonated resin surfactants

ABSTRACT

The surfactants of this invention are phenolic-formaldehyde resins that have been sulfomethylated with from 1-13 moles of sulfomethylation per 1000 grams of the starting resin and further modified by reaction with up to 20 moles, preferably 0.25 to 10 moles, per 1000 grams of starting resin of a blocking agent of the type X(CHR) m  (CH 2 ) n  Y, wherein X is a halogen, an activated double bond, epoxy ring or halohydrin, Y is a property group such as sulfonate, phosphonate, carboxylate or hydroxyl, R is another property group such as hydrogen, hydroxyl, mercaptan or amine, and n and m are integers from 0 to 5, with n or m being at least 1, to at least partially block the phenolic hydroxyl group of the resin. The phenolic-formaldehyde resin may also be cross-linked to tailor its molecular weight and then treated with urea or ammonia, if desired.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of our copending application, Ser. No.333,995, filed Feb. 20, 1973 now U.S. Pat. No. 3,870,681 issued Mar. 11,1975.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to modified phenolic-formaldehyde resinsurfactants. More specifically, this invention relates to modifiedphenolic-formaldehyde resin surfactants that have been further modifiedby blocking of the phenolic hydroxyl groups. Additionally, thisinvention relates to the use of these surfactants as dispersants indyestuffs.

2. The Prior Art

Phenolic resins have found widespread use in numerous areas, inparticular, molded and cast plastic articles, adhesives for plywood aslaminating resins and in thermal insulation to name a few. Because theseresins are versatile and inexpensive, numerous reactants have been usedto modify the resins in order to improve certain properties, forexample, dispersing ability, or to inhibit a property that isundesirable for certain uses.

By way of illustration of modifying phenolic-formaldehyde resins, thefollowing patents are cited. U.S. Pat. No. 3,065,039 to E. Komarek etal. describes sulfomethylating a phenol-formaldehyde resin and its useas a synthetic tanning agent. U.S. Pat. No. 2,076,624 to M. DeGroote isdirected to a process for breaking emulsions with phenol resins thathave been reacted with alkylene oxides. U.S. Pat. No. 2,658,885 to G. F.D'Alelio describes soluble copolymers of epoxyalkoxyhydrocarbon-substituted phenol-aldehyde resins useful in cements,impregnates, coatings, etc. U.S. Pat. No. 3,606,988 to K. Walz et al.teaches a process for dyeing nitrogen-containing fibers in the presenceof a dyeing auxiliary consisting of the reaction product of an alkyleneoxide and the condensation product of a phenolic compound, formaldehydeand an amine. The art cited is meant to show the state of the art and isnot intended to be all inclusive of phenolic modifications or theiruses.

It is, therefore, the general object of this invention to produce asulfomethylated phenolic-formaldehyde resin in which some or all of thefree phenolic hydroxyl groups are blocked. Another object of thisinvention is to produce a modified phenolic-formaldehyde resin useful asa surfactant. Still another object of this invention is to provide adyestuff composition containing a sulfomethylated phenolic-formaldehyderesin having some or all free hydroxyl groups blocked as a dispersingagent.

Further objects, features and advantages of this invention will beevident from the following detailed description of the invention.

SUMMARY OF THE INVENTION

The improved modified resin surfactant of this invention is awater-soluble phenolic-formaldehyde resin containing 1-13 moles ofsulfomethylation per 1000 grams by solids weight of starting resin andfurther modified by reaction with up to 20 moles, preferably from 2 to10 moles (per 1000 grams by solids weight of starting resin), of anagent of the type X(CHR)_(m) (CH₂)_(n) Y, wherein X is a halogen, anactivated double bond, epoxy ring or halohydrin, Y is a property groupsuch as sulfonate, phosphonate, carboxylate or hydroxyl, R is anotherproperty group such as hydrogen, hydroxyl, mercaptan or amine, and n andm are integers from 0 to 5 with n or m at least 1 to at least partiallyblock the phenolic hydroxyl. The surfactants may be cross-linked totailor molecular weight and treated with urea or ammonia. Thesesurfactants are useful in dyestuff compositions comprising an admixtureof a dye cake, i.e., disperse dyes or vat dyes, and up to 75% by weightof the surfactant or this invention.

DETAILED DESCRIPTION OF THE INVENTION

The surfactants of this invention are modified phenolic-formaldehyderesins. The phenolic-formaldehyde resins which are modified to make thedispersants of this invention are, in general, prepared by reacting aphenol and formaldehyde. Besides phenol, other phenolic-type startingmaterials may be employed, such as cresol, phenol-cresol mixtures, andresorcinol. For the purpose of this specification phenol will bereferred to, but it is understood to include any of thehereinabove-mentioned starting materials.

The type of reactions between formaldehyde and a phenol by way ofcondensation and/or polymerization is substantially different dependingupon whether these reactions are effected in the presence of an alkalinecatalyst or in the presence of an acid catalyst. Various catalyst can beutilized including both acids and bases. Alkaline catalysts commonlyused for catalyzing the pehnol-formaldehyde reaction are the oxides andhydroxides of alkaline earths and alkali metals, ammonia, and aminessuch as ethanolamine. Acid catalysts commonly used include mineral andorganic acids, for example, sulfuric or oxalic acid.

When an alkaline catalyst, such as sodium hydroxide, calcium hydroxide,barium hydroxide and others, are employed, the initial reaction consistsprimarily in the production of methylol substituents on the benzene ringof the phenol, and the reaction product initially produced is soluble inwater and in organic solvents. The reaction product in this condition isreferred to as an "A-stage resin." Such alkaline catalyzed products aregenerally referred to as "resoles." The A-stage resole is soluble inaqueous alkaline solutions. The A-stage resole is the preferred startingresin for preparation of the sulfomethylated phenolic-formaldehydedispersants of this invention. Further reaction results inpolymerization of the methylol phenols to form a product that isinsoluble in alkaline solution, and the reaction product in thiscondition is commonly referred to as being in the "B-stage." Furtherpolymerization at elevated temperatures results in the conversion of theB-stage resin into the thermoset condition in which it normally occursin manufactured products, this condition being generally referred to asthe "C-stage."

As distinguished from the resoles produced by alkaline catalyzedreaction between formaldehyde and a phenol, the presence of an acidcatalyst results in a different reaction mechanism, resulting in morehighly polymerized reaction products which are commonly referred to inthe art as "novolaks." Such novolaks do not possess the solubility inwater of the resoles, and are generally utilized by effecting a cure inthe presence of a substantial quantity of a curing agent, such ashexamethylene tetramine. In order to use a novolak resin as the startingresin to make the dispersants of this invention, it is adjusted to analkaline pH.

In a preferred practice of this invention, a phenol and aldehyde mixtureare heated in the presence of a catalytic amount of sodium hydroxide andbrought to the A-stage. It is conventional in the preparation of theresin to commingle a phenol with an aqueous solution of formaldehyde inthe molar ratio desired. For the alkaline catalyzed resins, such molarratio usually is in the order of 1.0 moles to 3.0 moles of formaldehydeper mole of phenol, preferably 1.3-2.0 moles of formaldehyde per mole ofphenol, and for preparing the resole conventional practice is to employan aqueous formaldehyde solution containing approximately 37% offormaldehyde, paraformaldehyde or other comparable aldehydes. About 0.1to 15% by weight of sodium hydroxide or other alkaline catalyst is addedto the composition for promoting the reaction for forming the A-stageresin. The reaction of phenol and formaldehyde takes place by heating ata temperature between 70°C. and 150°C. for 1/2 to 6 hours. By virtue ofthe water initially included in the reaction mixture and that which isformed during reaction, an A-stage resole as initially produced usuallycontains approximately 40 to 70% solids. It is to be noted that duringthis heating some cross-linking will occur with the production of water.Solids content of the starting resin as used herein, denotes the weightof the cross-linked resin obtainable from the resole solution as apercentage of the total weight of the resole solution

The phenol-formaldehyde resole is modified by adding to itsulfomethylation solubilizing groups. By the term "sulfomethylation" asused herein; it is meant either the sulfonation with sodium sulfite orsulfur dioxide of a hydroxy methyl phenol, or phenol with hydroxymethane sulfonate. The term "sulfomethylation" thus includes thesulfonation at a carbon atom.

When the phenolic-formaldehyde resins are reacted with the solubilizinggroup, sulfomethyl groups are introduced into the resin. The amount ofsulfomethylated groups may vary from about 1 up to about 13 moles ofsulfomethylation per 1000 grams of wet resin; however, generally only 1to 6 moles of sulfomethylation are added to get the desired watersolubility. It is thought that sulfomethylation occurs primarily in theortho- or paraposition of the phenolic ring.

To sulfomethylate, the phenolic-formaldehyde resin is preferably reactedwith formaldehyde or paraformaldehyde or the like and the alkali metalsalts of sulfurous acid in an alkaline medium under a wide variety ofreaction conditions. Thus, the temperature of the aqueous medium inwhich the reaction is carried out may be varied considerably. Thetemperatures need only be sufficient to bring about the introduction ofmethylol or sulfomethylol groups into the resin. Generally, temperaturesbetween about 30°C. to 130°C. may be used although temperatures between90°-95°C. are preferred. Lower temperatures require longer reactiontimes and in order to complete the reaction within a reasonable time,i.e., 2 to 8 hours, preferably 4 hours, the preferred temperatures areused. Examples of alkali metal salts of sulfurous acid which are usefulin this invention include sodium sulfite, potassium sulfite, sodiumbisulfite, potassium bisulfite, sodium metabisulfite, potassiummetabisulfite and the like. The alkali metal sulfite and bisulfitescontain one mole of combined SO₂ for each mole of the sulfite. Thealkali metal metabisulfites, on the other hand, contain 2 moles ofcombined SO₂ for each mole of the metabisulfite. Accordingly, onlyone-half molecular proportion of alkali metal metabisulfite is requiredto a given amount of combined SO₂ equivalent to the combined SO₂ in onemolecular proportion of alkali metal sulfites or bisulfites. Thepreferred alkali metal salts of sulfurous acid, for the purposes of thisinvention, are sodium sulfite and sodium metabisulfite.

The amount of the alkali metal salt of sulfurous acid, for example,sodium sulfite, used in relation to the aromatic ring residues in theresin determines the water-solubility of the reaction product formed, itbeing understood, of course, that formaldehyde is also used with suchsalt, as described above. Although strictly speaking the formaldehydeand alkali metal salt of sulfurous acid both influence thewater-solubility of the final product under acid conditions, the alkalimetal salt through introduction of sulfonate groups and the formaldehydethrough the formation of methylol groups, the alkali metal salt ofsulfurous acid exerts the primary solubilizing influence. The degree ofsolubility in water of the final product may be varied widely by properselection of the proportions of the alkali metal salt of sulfurous acidwith relation to the aromatic ring residues in the resole. Thus, it ispossible to use the sulfurous acid salt in an amount sufficient toprovide from 0.5 to 2.0 moles of combined SO₂ for each aromatic ringresidue (for example, phenol residue) in resin when products having highsolubility in water are desired. By decreasing the proportion of thealkali metal salt of sulfurous acid with relation to the aromatic ringresidues in the resin, the water-solubility of the product decreases andits salt sensitivity increases. Thus, if the sulfurous acid salt is usedin amounts sufficient to provide from about 0.15 to 0.90 moles ofcombined SO₂ for each aromatic ring residue in the resin, excellentdispersing agents are obtained. These agents have sufficientwater-solubility to be soluble in water which is acidic, neutral andalkaline. If the mole ratio of combined SO₂ in the sulfurous acid saltto aromatic ring residues in the resin is appreciably below 0.1, theproducts are substantially insoluble in neutral or acidic aqueous media.

The molecular proportions of formaldehyde, either as formalin, or asparaformaldehyde, and the alkali metal salt of sulfurous acid may bevaried widely with relation to each other and also with relation to thearomatic ring residues in the resin depending on the properties desiredin the dispersant. For most purposes, the mole ratio of formaldehyde tothe alkali metal salt of sulfurous acid is preferably at least one moleof formaldehyde for each mole of combined SO₂ in the alkali metal salt.If less formaldehyde is used, an excess of the alkali metal salt ofsulfurous acid remains in the reaction mixtures and does not take partin the reaction. Hence, the solids concentration of the reaction mixtureis increased without any corresponding benefit. Moreover, if thereaction mixture is neutralized at the end of the reaction, as isusually the case, more acid is required to neutralize the reactionmixture. Consequently, more salt is formed and the solids content of thefinal product is increased without any corresponding benefit in theproperties of the end product. When it is desired to cross-link theresin to the maximum possible extent, it is possible to increase theamount of formaldehyde substantially. In such a case, the mole ratio offormaldehyde to combined SO₂ in the alkali metal salt of sulfurous acidmay be as high as 25:1.

The pH of the reaction mixture will vary considerably depending on theparticular alkali metal salt of sulfurous acid used. Thus, with sodiumsulfite the pH will be higher initially than in the case where sodiumbisulfite or sodium metabisulfite is used. Moreover, since sodiumhydroxide is liberated during the reaction when sodium sulfite is usedand is not liberated in those instances when sodium bisulfite or sodiummetabisulfite is employed, the reaction mixture at the completion of thereaction will have a higher pH when sodium sulfite is used. Thealkalinity of the reaction mixture is normally derived from the alkalimetal salt of the sulfurous acid and it is not necessary to add alkalifor this purpose, especially when the amount of the alkali metal salt ofsulfurous acid used is sufficient to neutralize the acidity of the resinand the formalin solution. If the amount of the alkali metal salt ofsulfurous acid employed is not sufficient for such neutralization asmall amount of an alkali metal hydroxide is added to make the reactionmixture slightly alkaline. When sodium sulfite is used, thesulfomethylated phenolic-formaldehyde resin generally has a final pH ofbetween 9.5 and 12.0.

Since free formaldehyde and methylol groups are present, at least duringthe initial stages of the sulfomethylation reaction, a certain amount ofcross-linking of the resin takes place resulting in increased molecularweight. In dye dispersants, increased molecular weight is desirable upto a point to produce desirable dispersant properties. Additionalamounts of formaldehyde, say 0.2 to 1.0 moles of formaldehyde per 1000grams of sulfomethylated resin, may be used to effect cross-linking.Also heating, at say 90°C., for 1-3 hours promotes the formaldehydecross-linking which does not block the phenolic hydroxyl. Formaldehyde,for instance, is an effective cross-linking agent; whereas,epicholorohydrin is less effective. It should also be pointed out thattoo high a molecular weight, i.e., over 30,000, of the sulfomethylatedresin is undesirable. For the purposes of this specification the term"low molecular weight" refers to dispersants having a molecular weightless than 500; and "high molecular weight" refers to dispersants havinga molecular weight more than 15,000. Dispersants having a molecularweight between 2,000 and 20,000 are preferred.

After sulfomethylation of the resin and cross-linking is effected to thedesired level, an alkaline mixture or solution is obtained which may beused as such or neutralized with an acid or made acidic. If the solutionis neutralized or made acidic, it is preferably cooled prior to theaddition of acid to avoid high temperatures caused by the heat ofneutralization of alkali in the mixture. In the preparation of thedispersants of this invention, the pH of the final solution is usuallylowered with a mineral acid, such as sulfuric acid preferably togetherwith an organic acid, such as glycolic acid or acetic acid, as abuffering agent. In such instances the final pH of the solution isnormally adjusted between about 6 and 10. When a minimum amount of wateris used in the reaction mixture, the final solution is quite viscous.Such solutions may be diluted with water to increase their pumpabilityeither before or after they are neutralized.

It may be desirable to react the sulfomethylated, cross-linked,phenolic-formaldehyde resin with urea or ammonia after blocking iscompleted. This reaction allows a greater amount of sulfomethylation tobe effective by deactivating unreacted methylol groups, while stillmaintaining good heat stability. Generally, 0.5 to 7.5 moles of ammoniaor urea per 1000 grams of cross-linked, sulfomethylated resin is used ata temperature between 80°C. and 150°C. for from 5 minutes to 1 hour.

When products which are soluble in water under acid conditions aredesired, it is important to use sufficient water in the reaction mixtureto dissolve all of the reagents and the final product, otherwise thereaction does not proceed as rapidly as is desired and variousdifficulties are encountered. When the final solution is to be shipped,it is usually desirable to use the minimum amount of water in thereaction mixture.

The phenolic-formaldehyde resins are further modified by reaction withfrom up to 20 moles, preferably from 2 to 10 moles, per 1000 grams bysolids weight of starting resin with an agent of the type X(CHR)_(m)(CH₂)_(n) Y, wherein X is a halogen, an activated double bond, epoxyring or halohydrin, Y is a property group such as an alkane sulfonate,phosphonate, carboxylate or hydroxyl, R is another property group suchas hydrogen, hydroxyl, mercaptan, or amine, and n and m are integersfrom 0 to 5 and n or m is at least 1 to at least partially block thephenolic hydroxyl. The reaction of the resin with any of the reactantsserves primarily to lower the phenolic hydroxyl content of the resin.Depending upon the starting resin the acid hydroxyl content begins to beblocked by small amounts of reactant per 1000 grams of resin and can bereduced to substantially zero.

Examples of the blocking agents contemplated with the type exemplifiedby X(CH₂ R)_(m) (CH₂)_(n) Y, when m is 0, include for example, ethyleneoxide, propylene oxide, chloromethanesulfonate,chloromethanephosphonate, 2-chloroethanol, 2-bromoethanol and acrolein,among others. When m is 1 or more, blocking agents include, for example,1-chloro-2-hydroxyethane phosphonate and acrylamide. When X is ahalohydrin specific blocking agents include for example,3-chloro-2-hydroxypropane phosphonate, 3-chloro-1, 2-dihydroxypropane,and 3-chloro-2-hydroxypropane sulfonate, when Y is a phosphonate orhydroxyl respectively, R is a hydrogen, m is 1 and n is 0. More than oneblocking agent may be used in the same reaction to form the blockedresin. For example, epichlorohydrin and 3-chloro-2-hydroxypropanesulfonate may be reacted at the same time with the sulfomethylated resinto tailor an end product having particular properties.

It should also be pointed out that particularly good results areobtained when two or more dispersants are mixed together.

The blocked resins are made by simply dissolving the starting resin inwater and intermixing a given amount of blocking agent and reacting at atemperature between about 10°C. and 200°C. with the time depending uponthe temperature used and the degree of reaction desired. Typically, theblocked resin is neutralized, allowed to cool and then dried. Acatalyst, such as sodium hydroxide may be used if desired but is notnecessary.

The surfactants of this invention are particularly useful as dispersantswith disperse dyes or vat dyes in either the dry or liquid form. Theblocked resins may be added to the dye cake before, during or aftergrinding. For most dyeing applications a surfactant having 1 to 6 molesof blocking agent per 1000 grams of starting resin is used. It isgenerally preferred to add the surfactant prior to grinding so that itwill be thoroughly mixed and aid in particle size reduction. The amountof blocked resin dispersant added to a dye will vary widely, dependingupon the particular dye cake, the materials to be dyed and the effectdesired. Amounts up to 75% of the blocked resin dispersant, based uponthe weight of dried dye cake may be used. The most important factor indetermining the proper amount of blocked resin to the used in making upthe dyestuff is the particular dye cake used. Generally this amount willvary from dye to dye.

Dyestuff compositions comprise, for the most part, a dye cake, i.e.,disperse dyes or vat dyes, and a dispersant. These dyestuff compositionsare widely used to color both natural and synthetic fibers. The dyedispersants that may be used to disperse the dye cake vary widely inmethod of manufacture and source. In the dyestuff composition thedispersant serves three basic functions. It assists in reducing the dyeparticle to a fine size, it maintains a dispersing medium and it is usedas an inexpensive diluent. Generally, dye dispersants are of two majortypes, one of those being sulfonated lignins from the wood pulpingindustry via the sulfite or kraft process, the other being a watersoluble aromatic, i.e., napthalene sulfonate, from the petroleumindustry. The disadvantages of sulfonated lignins include fiberstaining, reduction if diazo type dyes, dark brown color and a tendencyto stabilize foams.

Fiber staining by the lignin occurs mainly on cellulosic and nitrogenousfibers such as cotton, nylon and wool; polyester fibers are also stainedbut to a lesser extent. A second disadvantage of sulfonated lignindispersants has been that when dyeing with diazo-type dyes under hightemperature and pressure dyeing processes, the oxidizable ligninstructures tend to reduce the diazo dye linkage. Another disadvantage isthe brown color. Lastly, foam stabilization properties are troublesomefor several reasons.

The advantages that water-soluble lignin dispersants possess over otherdispersants include the ability to impart better heat stability to thedye dispersion, and to disperse with equal effectiveness. Anotheradvantage of a water-soluble lignin dispersant is that it tends to actas a dye retarder. Some dyes have a tendency to start dyeing at very lowtemperatures. Dyers prefer colors to dye a fiber at a steady rateproportional to temperature increase. If the color dyes too rapidly, thegoods take on a streaky appearance; and creases in the material dye morerapidly than the face of the cloth.

The dispersants described herein possess excellent dispersionproperties, low color, no azo dye reduction tendencies, no fiberstaining properties and low viscosities at high solids contents.

As stated earlier, these modified water soluble resins are particularlyuseful dispersants (dyestuffs, pigments, etc.), as metal complexingagents (cement, nuclei growth control, water purification) and asemulsion stabilizers (asphalt, chemical impurities in dyestuffs,dyestuff carriers, etc.).

The practice of this invention may clearly be seen in the followingexamples.

EXAMPLE 1

This example illustrates a preferred process for making thesulfomethylated phenolic-formaldehyde resin used to make the dispersantsof this invention.

A resole resin was prepared by condensing 1 to 1.3 molar portions ofphenol to formaldehyde in the presence of a sodium hydroxide catalyst.The reaction was carried out at about 70°C. until the resin reached theA-stage. The A-stage resin had a solids content of 59.4% and a pH of 8.8with a major portion of the resin having a molecular weight of between125 and 1800. To a 1 gallon reactor kettle, 1512 grams of the resin werecharged. To this was added 600 grams of reagent grade Na₂ SO₃, 1200grams water and 372 grams of 37% formaldehyde. The contents werecontinuously stirred and heated to 90°-95°C. for 4 hours to effectsulfomethylation. The pH of this reaction, 10 minutes after heating wasdiscontinued, was 10.3

EXAMPLE 2

Samples of the sulfomethylated phenolic-formaldehyde resin of Example 1were reacted with ethylene oxide to make a resin in which the phenolichydroxyl groups are blocked. The conditions used were as follows. The pHof the sulfomethylated resin (1000 grams) was lowered to 9.5 with aceticacid (47 grams) and placed in a 2-liter stainless steel bomb and theentire contents frozen. Liquid ethylene oxide (47 grams) was added tothe bomb, after purging with nitrogen, and the bomb capped and heated to90°C. The pressure rose to approximately 3 atmospheres and then fell tozero soon after the 90°C. temperature was reached. The heating wasdiscontinued after 30 minutes at 90°C. Upon removing from the bomb thepH was 11.7. The process was repeated in order to add more ethyleneoxide to the resin. In order to keep hydrolysis of the ethylene oxide toa minimum, the multistage addition was used. When all the ethylene oxidedesired (usually between 1 and 6 moles) was added the pH was lowered to8.5 and 30 grams of urea were added. After 10-30 minutes at 90°C., 20grams of boric acid were added and the final pH adjusted to 8.0 withacetic acid if necessary.

                  TABLE I                                                         ______________________________________                                                  Maximum Possible                                                                             Moles EO/                                            Run No.   Blocking       1000 grams wet resin                                 ______________________________________                                        2         1              1                                                    3         2              2                                                    4         3              3                                                    5         4.5            4.5                                                  ______________________________________                                    

EXAMPLE 3

Samples of the sulfomethylated phenolic-formaldehyde resin of Example 1were reacted with varying ratios and amounts of epichlorohydrin and3-chloro-2-hydroxypropane sulfonate (CHP) to make a resin in which thephenolic hydroxyl groups are blocked. The conditions used in thesynthesis of these compounds are as follows. The CHP was added to theresin (1000 grams) to lower the pH to 9.5 (if the amount of CHP to beadded was not sufficient to lower the pH to 9.5 acetic acid was used).Water in the equivalent amount as the total CHP and epichlorohydrin tobe used was added to the reaction solution and the mixture was heated to80°C. under stirring. The epichlorohydrin was then added over a 5 to 10minute period. The rest of the CHP was then added and the pH adjustedbetween 9.5 and 10.0 with 50% sodium hydroxide solution. The mixture wasstirred and kept at 80°C. for 30 minutes and then heated to 90°C. andreacted for 60 minutes. At the end of the reaction period the pH wasdropped with acetic acid to 8.5 and 30 grams urea were added. After 10minutes at 90°C., 20 grams of boric acid were added and the final pHadjusted to 8.0 with acetic acid if necessary.

                  TABLE II                                                        ______________________________________                                                    Maximum        Moles/1000 grams wet resin                         Run         Blocking       (Example 1)                                        No.         Possible       CHP        epichlorohydrin                         ______________________________________                                        6           5.0             0         2.5                                     7           2.5            2.5        0                                       8           3.0            2.0        0.5                                     9           3.5            1.5        1.0                                     10          3.0            1.5        0.75                                    ______________________________________                                    

EXAMPLE 4

To illustrate other blocking agents, a number of other products wereprepared and tested as disperse dye dispersing agents (Table IV). Someof these products are shown in the following table. They were typicallyprepared using conditions similar to those given in Examples 2 and 3,except that higher temperatures and pressures were needed in runs 23-25in order to get reaction to occur.

                  TABLE III                                                       ______________________________________                                                                  Moles of Additive/                                                            1000 grams wet resin                                Run No. Blocking Additive (Example 1)                                         ______________________________________                                        11      propylene oxide   3                                                   12         "              4.5                                                 13      2-chloroethanol   1                                                   14         "              2                                                   15         "              3                                                   16         "              4                                                   17         "              6                                                   18         "              10                                                  19      chloroacetic acid 0.6                                                 20         "              1.2                                                 21         "              2.0                                                 22         "              6.0                                                 23      chloromethane phosphonate                                                                       1.0                                                 24         "              3.0                                                 25      chloromethane sulfonate                                                                         3.0                                                 ______________________________________                                    

EXAMPLE 5

In order to clearly illustrate the advantages in physical propertiesobtained by the dispersants of this invention they were tested asdisperse dyestuff dispersants. These tests were conducted according tothe test procedures outlined below.

A standard diazo disperse dye paste was prepared by adding DisperseBrown 1, C.I. 21000, (50 grams dry crude), dispersing agent (35 grams ondry solids basis) and water (to 40% solids) to a 1-quart ball mill.After milling 1 gram of solids material (2.5 grams liquid basis) wasmixed with 250 milliliters of tap water and poured through a Buchnerfunnel containing a tared, 9.0 cm., No. 4 Whatman filter paper (withvacuum). The paper was washed with 300 milliliters of tap water (120° to140°F.), dried, weighed and the residual dye material left on the filtercalculated. If residual materials is less than 0.01 grams the dispersionis called excellent, between 0.01 and 0.05 grams the dispersion isconsidered good, and anything above 0.05 grams residual is consideredpoor.

A thermosol test was also run to determine fiber staining. Thisprocedure involves padding a 65/35:dacron/cotton checkered cloth with a60 g/l dispersant solution. The cloth is then dried and thermosoled at210°C. for 90 seconds. The cloth is then treated with acaustic-dithionite solution (100°C.-30 sec.) and then oxidized in asodium perborate solution (10 minutes at 50°C.). The cloth is thenscoured in dilute soda ash (1 g/l) with a surfactant for 5 minutes at100°C. Finally the cloth is rinsed and dried at 105°C. The cotton wasfound to be more sensitive to stain than the polyester and results aredescribed in terms of stain on cotton fiber.

The test to determine the color value of the dispersant involvesmeasuring the absorption of a pH 6.0 dispersant solution at 280 and 500nm and then calculating an 68 ₅₀₀ value.

The diazo dye reduction test was performed by charging a pressure bombwith 500 mg of C.I? 21000, Disperse Brown C.I. 1 dye, 200 cc water, and20 grams of sulfonated dispersant. The mixture was thoroughly stirredand the pH adjusted to between 5 and 6 with acetic acid. A 10 gram nylonskein was placed in the dye mixture, the bomb sealed and heated to130°C. for 1 hour. After cooling, the skein was removed from the bomb,washed, dried and compared visually to a skein which had been similarlytreated except the sulfonated dispersant was omitted. If desired thereduction in color can be determined spectrometrically on the residualsolution.

                                      TABLE IV                                    __________________________________________________________________________           Blocking Agent                                                                             Dis- Fiber                                                                             Diazo                                            Run    and moles/1000                                                                             persion                                                                            Stain-                                                                            Dye   Color                                      No.    grams of Run No. 1                                                                         Results.sup.a                                                                      ing.sup.b                                                                         Reduction.sup.c                                                                     Value                                      __________________________________________________________________________     1.sup.d                                                                             no blocking  1    4   3     0.01                                        2     ethylene oxide - 1                                                                         1    4   --    0.0075                                      3     ethylene oxide - 2                                                                         1    3   --    0.0055                                      4     ethylene oxide - 3                                                                         1    2   --    0.0035                                      5     ethylene oxide - 4.5                                                                       2    1   --    0.0060                                      6     CHP - epi.sup.e 0:2.5                                                                      2    1   1     0.0025                                      7     CHP - epi.sup.e 2.5:0                                                                      1    1   2     0.0085                                      8     CHP - epi.sup.e 2.0:0.5                                                                    1    1   --    0.0050                                      9     CHP - epi.sup.e 1.5:1.0                                                                    1    1   1     --                                         10     CHP - epi.sup.e 1.5:0.75                                                                   1    1   --    0.0070                                     12     propylene oxide 4.5                                                                        1    --  --    --                                         13     2-chloroethanol 1                                                                          1    --  --    --                                         14     2-chloroethanol 2                                                                          1    --  --    --                                         16     2-chloroethanol 4                                                                          1    1   --    0.0065                                     17     2-chloroethanol 6                                                                          2    --  --    --                                         18     2-chloroethanol 10                                                                         3    --  --    --                                         20     chloroacetic acid 1.2                                                                      1    --  --    --                                         21     chloroacetic acid 2.0                                                                      1    3   --    --                                         22     chloroacetic acid 6.0                                                                      2    1   --    --                                         Reax 85A.sup.f      1    3   4     1.9                                        __________________________________________________________________________     Notes:                                                                        .sup.a 1 - indicates excellent dispersion, 5 indicates poor dispersion        .sup.b 1 - indicates no fiber staining, 5 indicates a great deal of fiber     staining.                                                                     .sup.c 1 - indicates no azo dye reduction, 5 indicates a great deal of az     dye reduction.                                                                .sup.d Product produced in Example 1 plus addition of urea (3g/100g wet       resin) and boric acid (2g/100g wet resin).                                    .sup.e CHP is 3-chloro-2-hydroxypropane sulfonate and epi is                  epichlorohydrin. Runs 8-10 are combinations of these products while 6 is      epi alone and 7 is CHP alone.                                                 .sup.f Reax 85A is a commercial disperse dye dispersant made of lignin.  

While the invention has been described and illustrated herein byreferences to various specific materials, procedures and examples, it isunderstood that the invention is not restricted to the particularmaterials, combinations of materials, and procedures selected for thatpurpose.

Numerous variations of such details can be employed, as will beappreciated by those skilled in the art.

What is claimed is:
 1. A dyestuff composition comprising, a disperse orvat dye cake and from 1 to 75% by weight of a water-soluble dispersanton said dyestuff composition, said water-soluble dispersant beingreaction products of sulfomethylated phenolic-formaldehyde resin and0.25 moles to 20 moles per 1000 grams of said resin of an agent of thetype X(CHR)_(m) (CH₂)_(n) Y, wherein X is a halogen, a halohydrin group,an activated double bond or an epoxide group, Y is a sulfonate,carboxylate, phosphonate or hydroxyl, mercaptan, amine or hydrogen, andn and m are integers from 0 to 5 with m and n together being at least 1,to give resin adducts with the phenolic hydroxyl at least partiallyblocked.
 2. The dyestuff composition of claim 1 wherein said resindispersant is reacted with from 1 to 10 moles of said agent per 1000grams of resin.
 3. The dyestuff composition of claim 1 wherein saidresin dispersant contains from 1 to 13 moles of sulfomethylation.
 4. Thedyestuff composition of claim 1 wherein said agent is chloromethanesulfonate.
 5. The dyestuff composition of claim 1 wherein said agent ischloroacetic acid.
 6. The dyestuff composition of claim 1 wherein saidagent is 3-chloro-2-hydroxypropane-sulfonate.
 7. The dyestuffcomposition of claim 1 wherein said agent is ethylene oxide.
 8. Thedyestuff composition of claim 1 wherein said agent is 2-chloroethanol.9. The dyestuff composition of claim 1 wherein said agent is propyleneoxide.
 10. The dyestuff composition of claim 1 wherein said agent isepichlorohydrin.
 11. The dyestuff composition of claim 1 wherein saidreaction products are formed by reacting more than one of said agents.12. A dyestuff composition comprising a disperse or vat dye cake andfrom 1 to 75% by weight of dispersant on said dyestuff composition, saiddispersant being a mixture of more than one blocked, water-soluble,sulfomethylated phenolic-formaldehyde resin of claim 1.